Graphic data copy sheet and method of using it



United States Patent 3,140,947 GRAPHIC DATA COPY SHEET AND METHOD OF USENG IT Peter L. Foris, Dayton, Ohio, assignor to The National Cash Register Company, Dayton, Ohio, a corporation of Maryland No Drawing. Filed Jan. 25, 1961, Ser. No. 84,749 8 Claims. (Cl. 96-48) This invention relates to a data-copy process and lightsensitive record sheet material therefor, and particularly pertains to such a process in which a copy of graphic material is made on such record sheet with visible light to produce an image, which sheet bearing the image is fixed by heat against further light coloration.

The invention is unique in that, in carrying out the process, all the ingredients on the copy sheet are dry; in that only visible light is necessary to produce a copy of the graphic material; and in that only moderate heat is required to fix the copy sheet.

The light-sensitive record sheet may be a pliable sheet material, such as paper, to which is applied, in the dark, as a solution in toluene or equivalent solvent, a mixture of a substantially colorless dye or dye intermediate, such as crystal violet lactone, and carbon tetrabromide, the sheet then being dried by evaporation of the solvent. The record sheet thus prepared is sensitive to visible light, and the sheet including the coloration produced by exposure to such light may be fixed by driving off the unused or unreacted carbon tetrabromide by heating the record material to a temperature between room temperature and about 100 degrees centigrade, depending on the dye.

The primary object of this invention is therefore to provide a light-sensitive record sheet material having thereon a dry mixture of ingredients which produce a darker distinctive color in areas subjected to visible light rays.

Another object is to provide a light-sensitive sheet as described in which the light-sensitive ingredients are inactivated by heat against further color change, thus insuring that subsequent exposure of the copy sheet to visible light will not affect the image formed by the first exposure of the copy sheet to visible light.

A further object is to provide a process for copying light-blocking graphic data disposed on master sheet material otherwise translucent Or transparent to visible light which includes the steps of (1) passing visible light through the transparent portions of the master sheet onto a novel light-sensitive copy sheet held in contact registery therewith, and (2) fixing the sheet, bearing the colored image formed in said first step, by heating the copy sheet to inactivate light-sensitive ingredients remaining on said sheet.

Any substantially colorless color-reactive materials, such as certain dyes and dye intermediates, which produce a distinctive color when exposed to visible light in the presence of carbon tetrabromide, the color being fixable by heat alone, may be used to sensitize the copy sheet of this invention.

Examples of such dyes and dye intermediates and derivatives which may be cited to illustrate but not to limit the invention include substantially colorless compounds such as color-reactive materials selected from the class consisting of (1) a triphenyl methane dye derivative, (2) a leuco methylene blue dye derivative, (3) a leucauramine dye derivative, (4) a xanthene dye derivative, and (5) the dihydril ether of Michlers hydrol. As specific 3,140,947 Patented July 14, 1964 examples of such materials within the scope of the classes mentioned above which are particularly suitable for the purposes of this invention, there may be mentioned the following, respectively: (1) 3,3-bis(dimethylaminophenyl)-o-dimethylaminophthalide, known also as crystal violet lactone, as disclosed in United States Reissue Patent No. 23,024; 3,3-bis(p-dimethylaminophenyl) phthalide, also known as malachite green lactone, and lower alkyl and halogen derivatives thereof, as disclosed in United States Patent No. 2,548,364; and 2-(p-nitrophenyl)-4,4- bis(p-dimethylaminophenyl) 7 dimethyl-amino-3, 1,4- benzoxazine (numbering follows Pattersons Ring Index, first edition, No. 947), having the structure (2) 10-benzoyl-3,7-bis(dimethylamino) phenothiazine, more commonly known as benzoyl leuco methylene blue, and halo and nitro derivatives thereof, as disclosed in United States Patents No. 2,784,186 and No. 2,783,228, respectively; naphthoyl leuco methylene blue, as disclosed in United States Patent No. 2,783,227; and the 10-noctanoyl, 10-(4-anisoyl), and IO-cinnamoyl analogs of benzoyl leuco methylene blue; (3) N-halophenyl and N- (alkylhalophenyl) leucauramine dyes as disclosed in United States Letters Patent No. 2,828,341 and No. 2,828,342, diethyl analogs of leucauramine compounds disclosed therein, and leucauramine derivatives having the general structural formula wherein R represents a substituent selected from the class consisting of amino, anilino, cyclohexyl (o-tolyl, p-tolyl, and 3-chloro-2-methyl phenyl and wherein each R is individually selected from the group consisting of -CH and C H radicals; (4) acetyl derivatives of 3,6'- bis(diethylamino) spiro [2,3-dihydrober1isosulfonazole- 3,9-xanthene], having the following structural formula:

Nil

and Z-(N-p-nitrophenyl), 3',6-bis(diethylamino) spiro [1,2,3H-phthalimidine-3,9'-xanthene], having the structural formula and (5) the dihydril ether of Michlers hydrol, more specifically [4,4,4",4" (oxydimethylidyne) tetrakis (N,N-dimethylaniline) disclosed in Chemical Abstracts, volume 47, page 1077a, and in Fierz-David, and Blangey, Fundamental Processes of Dye Chemistry, pages 138 and 139, Interscience Publishers Incorporated, New York, N.Y., United States of America, 1949.

In the process for making a copy of graphic data disposed on a master sheet which otherwise transmits visible light, such graphic data sheet is placed over the light-sensitive record copy sheet and transilluminated with visible light.

Light rays striking the graphic matter are either absorbed or reflected, so that little or no light is transmitted to the light-sensitive copy sheet in the areas in registry with said graphic matter; or, in some instances, only a fraction of the light incident on such graphic matter Will penetrate to form a graphic image area of intermediate density on the copy sheet, the density of which area depends on the amount of light penetrating said graphic area; that is to say, half-tone masters may be reproduced.

Light striking the master sheet in areas without graphic data is fully transmitted to a corresponding area on the light-sensitive coating on the copy sheet, the light-sensitive colorless color-reactive material in said coating turning to a distinctive color by a visible-light-induced reaction between said color-reactive material and carbon tetrabromide, such materials being in contact with each other.

Graphic copies thus formed on such visible-light-sensitive copy sheets are fixed by fixing the whole copy sheet against further change by exposure to visible light by subjecting the exposed copy sheet to a temperature ranging from slightly above room temperature to about 100 degrees centigrade, for a period of time suflicient to remove from the copy sheet the residual carbon tetrabromide not affected by the color-forming reaction. The amount of heat necessary for such removal obviously varies considerably; for example, in most carbon-tetrabromide-dye-base sheet combinations, removal of carbon tetrabromide is complete within a matter of seconds with ordinary record materials and heat sources, even at moderate temperatures. In other combinations, the copy sheet must be heated for longer periods due to variance rial such as gelatin or polyvinyl alcohol.

in heat conduction, amount of materials involved, and type of heat source.

The copy sheet containing the carbon-tetrabromidecolor-reactive-material mixtures of this invention is normally yellow in color. After controlled exposure of a sheet to visible light, those portions of the sheet which have not been subjected to said light retain the yellow color, but heating the copy sheet removes the yellow color, the color generally being replaced by a light-gray color, this background color change presumably being due to diminution of the carbon tetrabromide.

A color intensification of the image is produced by heating the copy sheet when certain combinations of carbon tetrabromide and colorless color-reactive materials are included on said sheet; for example, the blue-colored image formed by exposing to visible light a copy sheet containing a mixture of carbon tetrabromide and the dihydril ether of Michlers hydrol is intensified by such heating.

A preferred embodiment of the copy sheet of this invention consists of sheet material, such as a sheet of paper, organic polymer film, or the like, coated or impregnated, preferably in the dark, with a solution consisting of the following:

1 gram of crystal violet lactone (as disclosed in United States Patent No. Re. 23,024, which issued to Clyde S. Adams on August 17, 1948) 5 grams of carbon tetrabromide cc. of toluene The copy sheet is then dried by evaporation of the solvent.

As will be readily apparent to those skilled in the art, many combinations of materials may be utilized in the formation of the sensitized portion of the record material, be it a coating or an impregnating composition containing the light-sensitive ingredients of this invention. For example, suitable amounts of color-reactive materials and carbon tetrabromide may be dissolved in acetone and then added to an approximately ten percent aqueous solution of a hydrophilic polymeric film-forming mate Base material, such as paper, either coated or impregnated with the acetone composition of this example and then dried by evaporation of the solvent, provides a visible-lightsensitive copy sheet wherein the Visible-light-sensitivc ingredients are held dispersed in an essentially dry hydrophilic polymeric material binder carried by said base sheet material.

When a sheet of transparent or translucent sheet material having graphic matter to be copied disposed thereon is superimposed over the surface of a copy sheet as above described, a negative copy of the graphic matter is obtained on said copy sheet by merely directing visible light, as from an incandescent flood lamp, on and through the surface of the master sheet for a period of time sufiicient to provide the desired exposure of the copy sheet. The transmitted light rays activate the light-sensitive copy sheet to form a substantially colorless image of said graphic matter on a deeply colored background. Areas on the copy sheet which have not yet been exposed to light, and which, at this stage, are still sensitive to light, may be fixed and inactivated against further change to the effects of visible light by heating the copy sheet, preferably in the absence of light, to a temperature ranging from about 25 degrees centigrade to 100 degrees Centigrade, such as placing it on a hot plate or in an oven, or exposing it to infra-red rays until it is rendered unresponsive to further exposure to visible light.

The novel copy sheet of this invention also finds valuable application when used with a lens system which may serve to enlarge or reduce either a positive image or a negative image to be copied. In this system, the positive or negative to be copied is subjected to projected visible light rays, the projected rays being focused through a lens system through the master sheet onto the lightreactive surface of the copy sheet, thus providing either an enlarged image or a reduced image of the graphic material original, depending on the optics involved.

The specific disclosure of dyes used in conjunction with carbon tetrabromide is not to be deemed to limit the invention, as other dyes acting in the same manner are to be included within the broad scope of the claims to follow.

What is claimed is:

l. Light-sensitive copying material comprising a sheet support and having disposed on said support a composition which assumes a distinctive color when exposed to visible light, said composition consisting of (a) a substantially colorless color-reactive material selected from the class consisting of (1) a triphenyl methane dye selected from the group consisting of crystal violet lactone, malachite green lactone, and 2-(p-nitrophenyl)-4,4-bis (p dimethylaminophenyl) 7 dimethyl-amino-3,l,4- benzoxazine, (2) a lenco methylene blue dye selected from the group consisting of benzoyl, naphthoyl, 10-noctanoyl, l-(4-anisoyl), and IO-cinnamoyl leuco methylene blue; (3) a leucauramine dye having the following structural formula wherein R represents a substituent selected from the class consisting of N-(halophenyl), N-(alkylhalophenyl), amino, anilino, cyclohexyl, o-tolyl, ptoly1, and 3-chloro-2- methyl phenyl, and wherein each R is individually selected from the group consisting of -CH and C H radicals; (4) a xanthene dye selected from the group consisting of 2 N-acetyl, 3-6-bis(diethyl amino) spiro [2,3- dihydrobenzisosulfonazole-3 ,9xanthene] 2- (N-phenyl 3',6'-bis diethylamino) spiro [l,2,3H-phthalimidine-3,9- xanthene], and 2-(N-p-nitrophenyl), 3,6-bis(diethylamino) spiro [l,2,3H-phthalimidine-3,9-xanthene]; and (5) the dihydril ether of Michlers hydrol; and (b) carbon tetrabromide.

2. Light-sensitive copying material comprising a sheet support and having disposed on or within said support a composition which assumes a distinctive color when exposed to visible light, said composition consisting of (a) the substantially colorless material 3, 3-bis (4-dimethylaminophenyl)-6-dimethylaminophthalide and (b) carbon tetrabromide.

3. The light-sensitive copying material of claim 1 in which the substantially colorless material is the dihydril ether of Michlers hydrol.

4. A process for producing a copy of graphic data disposed on a master sheet translucent to visible light except for the graphic data, including the steps of passing visible light through the still-transparent areas of the master sheet onto a copy-receiving sheet having thereon, as an intimate mixture, a dried residue of carbon tetrabromide and a substantially colorless color-reactive material which turns to a distinctive strong color in the presence of said carbon tetrabromide when exposed to visible light, said material being selected from the class consisting of (1) a triphenyl methane dye selected from the group consisting of crystal violet lactone, malachite green lactone, and Z-(p-nitrophenyl)-4,4-bis(p-dimethyl aminophenyl)-7-dimethyl-amino-3,1,4-benzoxazine, (2) a leuco methylene blue dye selected from the group consisting of benzoyl, naphthoyl, IO-n-octanoyl, l0-(4-anisoyl), and IO-cinnarnoyl leuco methylene blue, (3) a leucauramine dye having the following structural formula wherein R represents a substituent selected from the class consisting of N-(halophenyl), N-(alkylhalophenyl), amino, anilino, cyclohexyl, o-tolyl, p-tolyl, and 3-chloro- 2-methyl phenyl, and wherein each R is individually selected from the group consisting of CH and -C H radicals, (4) a xanthene dye selected from the group consisting of 2 N-acetyl, 3,6'-bis(diethylamino) spiro [2,3- dihydrobenzisosulfonazole-3,9'-xanthene] 2- (N-phenyl) 3',6'-bis diethylamino) spiro [1,2,3H phthalimidine-3,9'- xanthene], and Z-(N-p-nitrophenyl), 3',6-bis(diethylamino) spiro [1,2,3H-phthalimidine-3,9'-xanthene], and (5) the dihydril ether of Michlers hydrol; whereby the graphic data appears on the copy sheet as uncolored areas on an otherwise distinctively colored sheet; and fixing the copy sheet by subjecting it to heat in absence of light, to remove the residue of the carbon tetrabromide constituent from said copy sheet.

5. A process for producing graphic data, including the steps of illuminating a copy sheet with an image of the graphic data in terms of visible light, the sheet containing intermixed, in the dry state, as the only photochemically active ingredients, carbon tetrabromide and 3,3-bis(4-dimethylarninophenyl) 6-dimethylaminophthalide which turns to a distinctive color when illuminated with visible light; and fixing the colored image on the copy sheet by subjecting the whole sheet to heat sufiicient to remove from said sheet the carbon tetrabromide which was not affected by the color-forming visible-light-sensitized reaction.

6. A light-sensitive copying process for producing permanent copies from a graphic original, consisting of (l) positioning a thin translucent pliable master sheet of material, having on one surface graphic data to be copied, said graphic data being defined in terms of areas which absorb visible light, in a smooth face-to-face relation with a copy sheet senstive to visible light, which copy sheet is provided with a composition colorable to a distinctive color by exposure to visible light, the composition consisting of a dry mixture of 3,3-bis(4-dimethylaminophenyl)-G-dimethylaminophthalide and carbon tetrabromide, (2) subjecting the two sheets so positioned to visible light rays so that said light will pass through the translucent master sheet, except where prevented from such passage by the light-absorbing areas, to provide a light pattern on the copy sheet which corresponds to the light transmitted through the master sheet, said light inducing a reaction in the light-sensitive composition which without perceptible delay results in the production of a distinctively colored image, and (3) fixing the colored image so formed by heating the copy sheet sufiiciently to inactivate the residual light-sensitive ingredients contained therein.

7. A process for producing a copy of graphic data existing on a translucent master sheet in terms of light- References Cited in the file of this patent blocking areas, including the step of exposing with visible UNITED STATES PATENTS light through said master sheet as a light mask, a copy 1,782,259 Eggert et aL 13 1930 sheet including a homogeneous mixture consisting of 5 2 344 4 5 Chaikley J ly 22 195 (a) 3,3-bis(4-dimethy1amino phenyl)-6-din1ethylamino- 3,042,515 Wainer July 3, 1962 phthalide, and (12) carbon tetrabromide. FOREIGN PATENTS 8. The process of claim 7 in which the copy sheet is fixed after the colored image appears thereon by the fur- 7 533: Great Bmam 1904 ther step of heating the copy sheet sufficiently to dissi- 10 2,462 Great Britain Jan. 31, 1907 pate the residual carbon tetrabromide as such. f 1907 

6. A LIGHT-SENSITIVE COPYING PROCESS FOR PRODUCING PERMANENT COPIES FROM A GRAPHIC ORIGINAL, CONSISTING OF (1) POSITIONING A THIN TRANSLUCENT PLIABLE MASTER SHEET OF MATERIAL, HAVING ON ONE SURFACE GRAPHIC DATA TO BE COPIED, SAID GRAPHIC DATA BEING DEFINED IN TERMS OF AREA WHICH ABSORB VISIBLE LIGHT, IN A SMOOTH FACE-TO-FACE RELATION WITH A COPY SHEET SENSITIVE TO VISIBLE LIGHT, WHICH COPY SHEET IS PROVIDED WITH A COMPOSITION COLORABLE TO A DISTINCTIVE COLOR BY EXPOSURE TO VISIBLE LIGHT, THE COMPOSITION CONSISTING OF A DRY MIXTURE OF 3,3-BIS(4-DIMETHYLAMINOPHENYL)-6-DIMETHYLAMINOPHTHALIDE AND CARBON TETRABROMIDE, (2) SUBJECTING THE TWO SHEETS SO POSITIONED TO VISIBLE LIGHT RAYS SO THAT SAID LIGHT WILL PASS THROUGH THE TRANSLUCENT MASTER SHEET, EXCEPT WHERE PREVENTED FROM SUCH PASSAGE BY THE LIGHT-ABSORBING AREAS, TO PROVIDE A LIGHT PATTERN ON THE COPY SHEET WHICH CORRESPONDS TO THE LIGHT TRANSMITTED THROUGH THE MASTER SHEET, SAID LIGHT INDUCING A REACTION IN THE LIGHT-SENSITIVE COMPOSITION WHICH WITHOUT PRECEPTIBLE DELAY RESULTS IN THE PRODUCTION OF A DISTINCTIVELY COLORED IMAGE, AND (3) FIXING THE COLORED IMAGE SO FORMED BY HEATING THE COPY SHEET SUFFICIENTLY TO INACTIVATE THE RESIDUAL LIGHT-SENSITIVE INGREDIENTS CONTAINED THEREIN. 